Organotemplate-free synthetic process for the production of a zeolitic material

ABSTRACT

The present invention relates to an organotemplate-free synthetic process for the production of a zeolitic material having a BEA framework structure comprising YO 2  and optionally comprising X 2 O 3 , wherein said process comprises the steps of (1) preparing a mixture comprising seed crystals and at least one source for YO 2 ; and (2) crystallizing the mixture; wherein Y is a tetravalent element, and X is a trivalent element, wherein the zeolitic material optionally comprises at least one alkali metal M, wherein when the BEA framework additionally comprises X 2 O 3 , the mixture according to step (1) comprises at least one source for X 2 O 3 , and wherein the seed crystals comprise zeolitic material having a BEA framework structure, preferably zeolite Beta.

This application is a continuation application of U.S. Ser. No.12/486,983 filed on Jun. 18, 2009.

The present invention relates to an organotemplate-free zeoliticmaterial with a BEA framework structure and to a process for theproduction of said material which does not involve the use of anorganotemplate. Furthermore, the present invention relates to the use ofan organotemplate-free zeolitic material having a BEA frameworkstructure in a catalytic process and/or in the treatment of exhaust gas.

The most prominent and best studied example for a zeolitic material witha BEA framework structure is zeolite Beta, which is a zeolite containingSiO₂ and Al₂O₃ in its framework and is considered to be one of the mostimportant nanoporous catalysts with its three-dimensional12-membered-ring (12MR) pore/channel system and has been widely used inpetroleum refining and fine chemical industries. Zeolite Beta was firstdescribed in U.S. Pat. No. 3,308,069 and involved the use of thetetraethylammonium cation as the structure directing agent. Althoughnumerous alterations and improvements have been made to the proceduresince then, including the use of other structure directing agents suchas dibenzyl-1,4-diazabicyclo[2,2,2]octane in U.S. Pat. No. 4,554,145 ordibenzylmethylammonium in U.S. Pat. No. 4,642,226, the known processesfor its preparation still relies on the use of organic templatecompounds. In U.S. Pat. No. 5,139,759, for example, it is reported thatthe absence of an organic template compound in the synthetic procedureof zeolite Beta leads to the crystallization of ZSM-5 instead.

In the synthesis of specialty zeolites in general, seed crystals areoften used as nucleating agents for improving the rate ofcrystallization, as well as for influencing the size and morphology ofthe resulting crystals. These, however, need not necessarily be the ofsame type of zeolite as the products obtained. U.S. Pat. No. 4,650,655,for example, teaches the use of ZSM-11, ZSM-50, or zeolite Beta seedcrystals in the synthesis of ZSM-5, in addition to tetrapropylammoniumas the structure directing agent.

A first drawback of the known production methods of zeolitic materialshaving a BEA framework structure such as zeolite Beta concerns thelengthy crystallization periods. U.S. Pat. No. 5,139,759, for example,discloses crystallization periods for zeolite Beta of 72 hours for anunseeded gel, and 66 and 68 hours with seeding. Although thecrystallization period can be further shortened by agitation, e.g. byusing rotating autoclaves, this involves considerably higher apparatusand maintenance costs and is therefore not feasible on the industrialscale.

Furthermore, the use of organic template compounds in the synthesis ofthese zeolitic materials possesses the major disadvantage that thetetraalkylammonium salts and other organic compounds employed thereinare expensive fine chemicals. In addition to this, the resultingproducts inevitably contains the organotemplates which are encapsulatedin the zeolitic framework created around them, such that a removal stepbecomes necessary in order to open the porous volume of the material foractual utilization, e.g. in catalysis.

Complete removal of the organic template compound, however, is difficultand is normally only achieved by calcination at higher temperatures,normally at 200-930° C. or even higher. This procedure not only greatlyincreases the production costs since the organic template is destroyedin the process and may not be recycled, it also further increases theproduction time results in excess energy consumption, and producesharmful gases and other unwanted waste products.

In addition to these major disadvantages, the harsh thermal treatmentultimately limits the production to thermally stable zeolite Beta, inparticular to high-silica zeolite Beta. Although ion-exchange methodshave been developed as an environmentally friendly alternative tocalcination for removing the organotemplate, only part of the organictemplates may successfully be recycled, the remainder interacting toostrongly with the zeolite framework for removal.

Thus, although-zeolitic materials having a BEA framework structure suchas zeolite Beta exhibit excellent properties in a series of catalyticreactions, their further potential applications are still greatlylimited due to the use of organic templates in the synthesis thereof.

In Xiao et al. “Organotemplate-free and Fast Route for Synthesizing BetaZeolite”, Chem. Mater. 2008, 20, 4533-4535 and Supporting Information, aprocess for the synthesis of zeolite Beta is described, in whichcrystallization of an aluminosilicate gel is conducted using zeoliteBeta seed crystals. In particular, an aluminosilicate gel is preparedstarting from fumed silica as the silica source, sodium hydroxide,sodium aluminate, and water, wherein said gel is then crystallized in anautoclave for 17 to 19 h at a temperature of 140° C. There is, however,no indication whatsoever in said document relating to the use ofdifferent starting materials for the preparation of an aluminosilicategel, nor does said document indicate the possibility of includingelements suited for isomorphous substitution in the mixture forcrystallization.

It was therefore an object of the present invention to provide a processfor the organotemplate-free synthesis of zeolitic material having a BEAframework structure.

It was also an object of the present invention to provide a process forthe production of organotemplate-free zeolitic material having a BEAframework structure which can be conducted under mild conditions and isnon-destructive towards the zeolite architecture. In particular, it wasalso an object to provide a process for the production of such materialswhich does not involve a high-temperature calcination treatment or othertreatment for the removal of organotemplates present in the frameworkstructure.

A further object of the present invention was to provide an improved andcost-effective process for the production of organotemplate-freezeolitic materials having a BEA framework structure, in particular withrespect to crystallization time, energy consumption, and environmentalpollution.

In addition to this it was also an object of the present invention toprovide organotemplate-free zeolitic materials having a BEA frameworkstructure which display an intact architecture as directly obtained fromthe crystallization process.

A further object of the present invention was to provide novel zeoliticmaterials having a BEA framework structure, in particular zeoliticmaterials which can advantageously be employed, for example, ascatalysts and/or catalyst supports.

According to the present invention it has surprisingly been found that azeolitic material having a BEA framework structure can be obtainedwithout using an organotemplate in the synthesis thereof. In particular,it has been found that when using seed crystals of a zeolitic materialhaving a BEA framework structure in the synthetic process,organotemplate-free zeolitic materials having a BEA framework structurecan be obtained without having to use an organotemplate in theirproduction. Thus, a one-pot synthetic procedure is provided for directlyobtaining a zeolitic material having a BEA framework, wherein theporosity is directly given and must not first be provided by one or morepost-synthetic treatments for removing structure directing agents fromthe crystallized framework.

Furthermore, it has surprisingly been found that besides providing amethod for the direct synthesis of an organotemplate-free zeoliticmaterial having a BEA framework structure, the inventive process allowsconsiderable reduction of the crystallization time compared to processeswhich rely on the use of an organotemplate. Consequently, the inventiveprocess is not only environmentally friendly but also greatly reducesboth the time and costs of production.

In addition to these considerable advantages, it has surprisingly beenfound that according to the inventive process, novel zeolitic materialshaving a BEA framework structure can be obtained displaying novelproperties which can be advantageously utilized in current and novelapplications. In particular, BEA frameworks are accessible, of which thechemical composition and/or physical properties thereof may not beobtained by organotemplate-mediated synthesis. In this respect, it hasquite unexpectedly been found that the inventive process can lead tozeolitic materials having a BEA framework structure which are enrichedwith respect to a particular polymorph compared to the products ofsynthetic procedures which rely on the use of an organotemplate.Furthermore, in the X-ray powder diffraction pattern of the novelzeolitic materials having a BEA framework structure at least in part ofthe reflections are noticeably shifted in their 2° Theta values comparedto the X-ray powder diffraction pattern of a zeolitic material having aBEA framework structure obtained from an organotemplate-mediatedsynthetic procedure.

In particular, with respect to a process for the organotemplate-freesynthesis of zeolite Beta as described in Xiao et al., it hassurprisingly been found that it is possible to incorporate furtherelements into the mixture for crystallization, thus leading toisomorphous substitution of Si and/or Al in the zeolite framework in asimple one-pot synthetic process. Thus, it has been found that the costintensive and time consuming steps of isomorphous substitution conductedafter the crystallization of zeolite Beta may presently be eliminated ina simple synthetic procedure. In addition to this, the one-pot syntheticprocedure according to the present invention avoids any harsh treatmentof the zeolite architecture usually inherent to such post-syntheticisomorphous substitution procedures.

Furthermore, it has surprisingly been found that the use of new startingmaterials as the silica source in an organotemplate-free syntheticprocedure may further reduce the crystallization time compared to aprocedure as taught in Xiao et al., wherein fumed silica is solelytaught as the silica source.

Therefore, the present invention relates to a process for theorganotemplate-free synthesis of a zeolitic material having a BEAframework structure comprising YO₂ and optionally comprising X₂O₃,wherein said process comprises the steps of

(1) preparing a mixture comprising seed crystals and at least one sourcefor YO₂; and

(2) crystallizing the mixture,

wherein Y is a tetravalent element, and X is a trivalent element,

wherein the zeolitic material optionally comprises at least one alkalimetal M,

wherein when the BEA framework additionally comprises X₂O₃, the mixtureaccording to step (1) comprises at least one source for X₂O₃, and

wherein the seed crystals comprise zeolitic material having a BEAframework structure, preferably zeolite Beta.

According to the inventive process, at no point does the mixtureprovided in step (1) and crystallized in step (2) contain more than animpurity of an organic structure directing agent specifically used inthe synthesis of zeolitic materials having a BEA framework structure, inparticular specific tetraalkylammonium salts and/or relatedorganotemplates such as tetraethylammonium and/or dibenzylmethylammoniumsalts, and dibenzyl-1,4-diazabicyclo[2,2,2]octane. Such an impurity can,for example, be caused by organic structure directing agents stillpresent in seed crystals used in the inventive process. Organotemplatescontained in seed crystal material may not, however, participate in thecrystallization process since they are trapped within the seed crystalframework and therefore may not act structure directing agents withinthe meaning of the present invention.

Furthermore, YO₂ and optionally X₂O₃ are comprised in the BEA frameworkstructure as structure building elements, as opposed to non-frameworkelements which can be present in the pores and cavities formed by theframework structure and typical for zeolitic materials in general.

According to the present invention, a zeolitic material having a BEAframework structure is provided in step (2). Said material comprisesYO₂, wherein Y stands for any conceivable tetravalent element, Ystanding for either one or several tetravalent elements. Preferredtetravalent elements according to the present invention include Si, Sn,Ti, Zr, and Ge, and combinations thereof. More preferably, Y stands forSi, Ti, or Zr, or any combination of said trivalent elements, even morepreferably for Si and/or Sn. According to the present invention, it isparticularly preferred that Y stands for Si.

Furthermore, according to the process of the present invention YO₂ canbe provided in step (1) in any conceivable form, provided that azeolitic material having a BEA framework structure comprising YO₂ can becrystallized in step (2). Preferably, YO₂ is provided as such and/or asa compound which comprises YO₂ as a chemical moiety and/or as a compoundwhich (partly or entirely) is chemically transformed to YO₂ during theinventive process. In preferred embodiments of the present invention,wherein Y stands for Si or for a combination of Si with one or morefurther tetravalent elements, the source for SiO₂ provided in step (1)can be any conceivable source. There can therefore be used, for example,all types of silica and silicates, preferably fumed silica, silicahydrosols, reactive amorphous solid silicas, silica gel, silicic acid,water glass, sodium metasilicate hydrate, sesquisilicate or disilicate,colloidal silica, pyrogenic silica, silicic acid esters, ortetraalkoxysilanes, or mixtures of at least two of these compounds.

In preferred embodiments of the inventive process, wherein the mixtureaccording to step (1) comprises at least one source for SiO₂, saidsource preferably comprises at least one compound selected from thegroup consisting of silica and silicates, preferably silicates, morepreferably alkali metal silicates. Among the preferred alkali metalsilicates, the at least one source preferably comprises water glass,more preferably sodium and/or potassium silicate, and more preferablysodium silicate. In particularly preferred embodiments of the presentinvention, the source for SiO₂ is sodium silicate. Furthermore, inembodiments comprising silica, fumed silica is preferred.

In particular, it has surprisingly been found that when the at least onesource for SiO₂ comprises water glass, crystallization is accelerated.This especially applies when water glass is the only source for SiO₂used in the inventive process.

Further preferred are embodiments wherein the zeolitic material having aBEA framework structure further comprises X₂O₃, wherein X stands for anyconceivable trivalent element, X standing for either one or severaltrivalent elements. Preferred tetravalent elements according to thepresent invention include Al, B, In, and Ga, and combinations thereof.More preferably, Y stands for Al, B, or In, or any combination of saidtrivalent elements, even more preferably for Al and/or B. According tothe present invention, it is particularly preferred that X stands forAl.

If, for example, boron is incorporated, for example free boric acidand/or borates and/or boric esters, such as, for example, triethylborate or trimethyl borate, can be used as starting materials.

According to preferred embodiments of the present invention, wherein thezeolitic material having a BEA framework structure comprises X₂O₃, atleast one source for X₂O₃ is provided in step (1). In general, X₂O₃ canbe provided in any conceivable form, provided that a zeolitic materialhaving a BEA framework structure comprising X₂O₃ can be crystallized instep (2). Preferably, X₂O₃ is provided as such and/or as a compoundwhich comprises X₂O₃ as a chemical moiety and/or as a compound which(partly or entirely) is chemically transformed to X₂O₃ during theinventive process.

In more preferred embodiments of the present invention, wherein X standsfor Al or for a combination of Al with one or more further trivalentelements, the source for Al₂O₃ provided in step (1) can be anyconceivable source. There can be used for example any type of aluminaand aluminates, aluminum salts such as, for example, alkali metalaluminates, aluminum alcoholates, such as, for example, aluminumtriisopropylate, or hydrated alumina such as, for example, aluminatrihydrate, or mixtures thereof. Preferably, the source for Al₂O₃comprises at least one compound selected from the group consisting ofalumina and aluminates, preferably aluminates, more preferably alkalimetal aluminates. Among the preferred alkali metal aluminates, the atleast one source preferably comprises sodium and/or potassium aluminate,more preferably sodium aluminate. In particularly preferred embodimentsof the present invention, the source for Al₂O₃ is sodium aluminate.

According to particularly preferred embodiments of the inventiveprocess, the mixture according to step (1) comprises at least onesilicate as a source for YO₂ and at least one aluminate as a source forX₂O₃, more preferably at least one alkali metal silicate and/or at leastone alkali metal aluminate, and even more preferably at least one waterglass, wherein the alkali metal of said preferred embodiments preferablycomprises sodium and/or potassium, more preferably sodium, and whereinthe alkali metal even more preferably is sodium.

In preferred embodiments of the inventive process wherein the mixtureaccording to step (1) comprises at least one source for X₂O₃, theYO₂:X₂O₃ molar ratio of the mixture can have any conceivable value,provided that a zeolitic material having a BEA framework structurecomprising both YO₂ and X₂O₃ is crystallized in step (2). Generally, themolar ratio ranges from 1 to 100, preferably from 5 to 85, morepreferably from 10 to 60, more preferably from 20 to 55, more preferablyfrom 25 to 50, and particularly preferably from 35 to 45. Furtherpreferred are embodiments wherein the YO₂:X₂O₃ molar ratio of themixture ranges from 15 to 40, more preferably from 20 to 35, and evenmore preferably from 25 to 30.

In embodiments of the present invention which are further preferred, thezeolitic material obtained and/or obtainable and/or the inventivematerial as such according to the inventive process comprises at leaston alkali metal M, preferably sodium and/or potassium, and morepreferably sodium. The alkali metal can be added at any conceivablestage of the inventive process, wherein preferably it is also added instep (1). More preferably, the entire quantity of the alkali metalcomprised in the zeolitic material having a BEA framework structure isadded in step (1) of the inventive process. In particularly preferredembodiments of the inventive process, the alkali metal is partly orentirely contained in the at least one source for YO₂ and/or X₂O₃provided in step (1), wherein preferably, the alkali metal is entirelycontained therein.

In general, the alkali metal M can be contained in the mixture accordingto step (1) of the inventive process in any conceivable amount, providedthat a zeolitic material having a BEA framework structure iscrystallized in step (2). Preferably, the M:YO₂ molar ratio in themixture according to step (1) ranges from 0.1 to 2, more preferably from0.2 to 1, more preferably from 0.3 to 0.9, and even more preferably from0.45 to 0.75.

According to preferred embodiments of the inventive process, the mixtureaccording to step (1) comprises at least one source for X₂O₃ and atleast one alkali metal M. In general, any conceivable amounts of thesecomponents can be contained in the mixture provided that a zeoliticmaterial having a BEA framework structure is crystallized in step (2).Preferably, the YO₂:X₂O₃:M molar ratios in the mixture according to step(1) range from (1-100):1:(2-90), more preferably from (5-85):1:(5-70),more preferably from (10-60):1:(8-50), more preferably from(20-55):1:(11-40), more preferably from (25-50):1:(13-35), and even morepreferably from (35-45):1:(15-30).

According to the process of the present invention, the mixture providedin step (1) can contain one or more sources for hydroxide anions OH⁻. Ingeneral any conceivable source for OH⁻ can be used, wherein the at leastone source preferably comprises a metal hydroxide, more preferably ahydroxide of an alkali metal M, more preferably sodium and/or potassiumhydroxide, and even more preferably sodium hydroxide. In preferredembodiments of the inventive process, wherein the mixture comprises asilicate as a source for YO₂ and/or an aluminate as a source for X₂O₃,it is particularly preferred that the mixture does not contain a sourcefor OH⁻.

In general the OH⁻:YO₂ molar ratio of the mixture according to step (1)of the inventive process can have any conceivable value, provided that azeolitic material having a BEA framework structure is crystallized instep (2). Preferably, said molar ratio ranges from 0.1 to 1, morepreferably from 0.2 to 0.9, more preferably from 0.3 to 0.7, morepreferably from 0.4 to 0.65, and even more preferably from 0.43 to 0.62.

According to the process of the present invention, seed crystals areprovided in step (1), wherein said seed crystals comprise a zeoliticmaterial having a BEA framework structure. In general, said seedcrystals can comprise any zeolitic material having a BEA frameworkstructure, provided that a zeolitic material having a BEA frameworkstructure is crystallized in step (2). Preferably, the zeolitic materialhaving a BEA framework structure comprised in the seed crystals is azeolitic material obtained according to the inventive process. Morepreferably, the zeolitic material having a BEA framework structurecomprised in the seed crystals is the same as the zeolitic materialhaving a BEA framework structure which is then crystallized in step (2).Particularly preferred are seed crystals comprising zeolite Beta, morepreferably zeolite Beta which has been obtained according to theinventive process. In particularly preferred embodiments, the seedcrystals are zeolite Beta crystals, preferably zeolite Beta crystalsobtained according to the inventive process.

According to the inventive process, any suitable amount of seed crystalscan be provided in the mixture according to step (1), provided that azeolitic material having a BEA framework structure is crystallized instep (2). In general, the amount of seed crystals contained in themixture according to step (1) ranges from 0.1 to 50 wt.-% based on 100wt.-% of YO₂ in the at least one source for YO₂, preferably from 0.5 to40 wt.-%, more preferably from 1 to 35 wt.-%, more preferably from 2 to25 wt.-%, more preferably from 3 to 20 wt.-%, and particularlypreferably from 5 to 15 wt.-%. Further preferred according to theinventive process is an amount of seed crystals ranging from 15 to 45wt.-%, more preferably from 20 to 40 wt.-%, and even more preferablyfrom 25 to 35 wt.-%.

In step (1) according to the present invention, the mixture can beprepared by any conceivable means, wherein mixing by agitation ispreferred, preferably by means of stirring.

In preferred embodiments of the present invention, the mixture accordingto step (1) of the inventive process further comprises a solvent. Anyconceivable solvent can be used in any conceivable amount, provided thata zeolitic material having a BEA framework structure can be crystallizedin step (2). Preferably, the solvent comprises water, wherein theH₂O:YO₂ molar ratio of the mixture ranges from 1 to 100, preferably from2 to 60, more preferably from 5 to 50, more preferably from 7 to 45,more preferably from 10 to 30, and particularly preferably from 15 to25. According to the inventive process, it is further preferred that theH₂O:YO₂ molar ratio of the mixture ranges from 15 to 45, more preferablyfrom 20 to 40, and even more preferably from 25 to 35. In particularlypreferred embodiments, the solvent provided in step (1) is distilledwater.

In preferred embodiments of the process of the present invention, themixture according to step (1) further comprises at least one source ofat least one element suitable for isomorphous substitution of at least aportion of the Y atoms and/or of the X atoms in the BEA frameworkstructure. In general, any conceivable element can be used. In preferredembodiments, the at least one element is selected from the groupconsisting of Cu, Co, Cr, Ni, Fe, V, and Nb, preferably from the groupconsisting of Cu, Co, Cr, Ni, Fe, more preferably from the groupconsisting of Cu and Fe, wherein even more preferably the at least oneelement is Fe. In a particularly preferred embodiment, the at least oneelement suitable for isomorphous substitution is Fe.

In particularly preferred embodiments of the present invention, themixture according to step (1) comprises at least one silicate and/or atleast one aluminate in addition to the at least one element suitable forisomorphous substitution, wherein preferably the at least one element isFe, and more preferably said at least one element is Fe.

Therefore, the present invention also provides a one-pot syntheticprocedure for the preparation of an organotemplate-free zeoliticmaterial having a BEA framework structure, preferably anorganotemplate-free zeolitic material which is isomorphously substitutedby Fe, wherein isomorphous substitution is not achieved by conventionalprocesses involving the post-synthetic treatment of an existingframework, wherein framework elements are treated such that they may bereplaced with other atoms which are then contained in the resultingframework structure. In particular, according to the inventive processit is not necessary to remove existing framework atoms for producing anisomorphously substituted framework structure.

Consequently, the present invention also relates to a one-pot syntheticprocedure for the production of an organotemplate-free zeolitic materialhaving a BEA framework structure, wherein at least a portion of the Yatoms and/or of the X atoms in the BEA framework structure isisomorphously substituted by at least one element, wherein the at leastone element is preferably selected from the group consisting of Cu, Co,Cr, Ni, Fe, V, and Nb, more preferably wherein the at least one elementis Fe.

In general, according to step (1) of the inventive process, the molarratio of YO₂ to the element or to the sum of elements suitable forisomorphous substitution can have any conceivable value, wherein themolar ratio preferably ranges from 5 to 300, more preferably from 10 to200, more preferably from 30 to 150, more preferably from 40 to 100, andeven more preferably from 50 to 90.

In general, the single components for providing the mixture of step (1)of the inventive process can be added in any order, provided that azeolitic material having a BEA framework structure is crystallized fromthe mixture in step (2). This may, for example, involve the addition ofthe optional solvent and optionally the at least one source for X₂O₃and/or the at least one source for OH⁻, followed by the addition of theat least one source for YO₂, wherein the seed crystals are only added tothe mixture afterwards. Alternatively, the addition of the optionalsolvent and optionally the at least one source for X₂O₃ and/or the atleast one source for OH⁻ may be first followed by the addition of theseed crystals, wherein the at least one source for YO₂ is only addedthereafter. The at least one source of at least one element suitable forisomorphous substitution optionally present in the mixture provided instep (1) may also be added at any point, provided that a zeoliticmaterial having an isomorphously substituted BEA framework structurewith respect to Y and/or optionally with respect to X is crystallizedfrom the mixture in step (2). By way of example, the at least one sourcefor isomorphous substitution may be added after the addition of theoptional solvent and optionally the at least one source for X₂O₃ and/orthe at least one source for OH⁻, and before the addition of the at leastone source for YO₂ and/or before the addition of the seed crystals.Alternatively, the at least one source for isomorphous substitution maybe added before or after the aforementioned components of the mixtureaccording to step (1).

In general, step (2) according to the inventive process can be conductedin any conceivable manner, provided that a zeolitic material having aBEA framework structure is crystallized from the mixture according tostep (1). The mixture can be crystallized in any type of vessel, whereina means of agitation is preferably employed, preferably by rotation ofthe vessel and/or stirring, and more preferably by stirring the mixture.

According to the inventive process, the mixture is preferably heatedduring at least a portion of the crystallization process in step (2). Ingeneral, the mixture can be heated to any conceivable temperature ofcrystallization, provided that a zeolitic material having a BEAframework structure is crystallized from the mixture. Preferably, themixture is heated to a temperature of crystallization ranging from 80 to200° C., more preferably from 90 to 180° C., more preferably from 95 to170° C., more preferably from 100 to 160° C., more preferably from 110to 150° C., and even more preferably from 115 to 145° C. Also preferredaccording to the inventive process are temperatures of crystallizationranging from 120 to 160° C., more preferably from 130 to 150° C., andeven more preferably from 135 to 145° C.

The preferred heating in step (2) of the inventive process can beconducted in any conceivable manner suitable for the crystallization ofa zeolitic material having a BEA framework structure. In general,heating my be conducted at one temperature of crystallization or varybetween different temperatures. Preferably, a heat ramp is used forreaching the temperature of crystallization, wherein the heating ratepreferably ranges from 10 to 100° C./h, more preferably from 20 to 70°C./h, more preferably from 25 to 60° C./h, more preferably from 30 to50° C./h, and even more preferably from 35 to 45° C./h.

In preferred embodiments of the present invention, the mixture accordingto step (1) is subjected in step (2) to a pressure which is elevatedwith regard to normal pressure. The term “normal pressure” as used inthe context of the present invention relates to a pressure of 101,325 Pain the ideal case. However, this pressure may vary within boundariesknown to the person skilled in the art. By way of example, this pressurecan be in the range of from 95,000 to 106,000 or of from 96,000 to105,000 or of from 97,000 to 104,000 or of from 98,000 to 103,000 or offrom 99,000 to 102,000 Pa.

In preferred embodiments of the inventive process wherein a solvent ispresent in the mixture according to step (1), it is furthermorepreferred that heating in step (2) is conducted under solvothermalconditions, meaning that the mixture is crystallized under autogenouspressure of the solvent which is used for example by conducting heatingin an autoclave or other crystallization vessel suited for generatingsolvothermal conditions. In particularly preferred embodiments whereinthe solvent comprises or consists of water, preferably of distilledwater, heating in step (2) is accordingly preferably conducted underhydrothermal conditions.

The apparatus which can be used in the present invention forcrystallization is not particularly restricted, provided that thedesired parameters for the crystallization process can be realized, inparticular with respect to the preferred embodiments requiringparticular crystallization conditions. In the preferred embodimentsconducted under solvothermal conditions, any type of autoclave ordigestion vessel can be used, wherein a Teflon-lined apparatus ispreferred.

In general, the duration of the crystallization process in step (2) ofthe inventive process is not particularly limited. In preferredembodiments involving heating of the mixture according to step (1), saidcrystallization process is conducted for a period ranging from 2 to 100h, more preferably from 8 to 70 h, and even more preferably from 13 to60 hours. According to the inventive process, it is further preferredthat crystallization is conducted for a period ranging from 10 to 30 h,more preferably from 12 to 25 h, and even more preferably from 14 to 20h. Furthermore, it is preferred that crystallization is conducted for aperiod ranging from 35 to 65 h, more preferably from 40 to 60 h, andeven more preferably from 45 to 55 h. According to a particularlypreferred embodiment of the present invention, crystallization isconducted for a period ranging from 10 to 16.5 h, more preferably from12 to 16 h, and even more preferably from 14 to 15.5 h.

According to preferred embodiments of the present invention, wherein themixture is heated in step (2), said heating may be conducted during theentire crystallization process or during only one or more portionsthereof, provided that a zeolitic material having the BEA frameworkstructure is crystallized. Preferably, heating is conducted during theentire duration of crystallization.

Thus, according to a particularly preferred embodiment of the inventiveprocess, Y stands for Si and the mixture according to step (1) furthercomprises at least one source for X₂O₃ wherein X is Al, and wherein theSiO₂:Al₂O₃ molar ratio of the mixture according to step (1) ranges from20 to 55, preferably from 25 to 50, and more preferably from 35 to 45.Furthermore, according to said particularly preferred embodiment, themixture further comprises at least one source for hydroxide anions,preferably a metal hydroxide, more preferably a hydroxide of an alkalimetal M, and even more preferably sodium hydroxide, wherein the OH⁻:SiO₂molar ratio of the mixture preferably ranges from 0.3 to 0.7, morepreferably from 0.4 to 0.65, and even more preferably from 0.43 to 0.62.In addition to this, the mixture according to said particularlypreferred embodiment comprises a solvent which is preferably distilledwater, and the mixture of step (1) is crystallized under hydrothermalconditions in step (2) at a temperature ranging from 120 to 160° C.,more preferably from 130 to 150° C., and even more preferably from 135to 145° C., and said heating is conducted for a duration ranging from 10to 30 h, more preferably from 12 to 25 h, and even more preferably from14 to 20 h.

Further preferred according to said embodiment is an H₂O:SiO₂ molar inthe mixture according to step (1) of 10 to 30, more preferably from 15to 25, and/or an amount of seed crystals ranging from 3 to 20 wt.-%,more preferably from 5 to 15 wt.-%.

According to a further embodiment of the inventive process which isparticularly preferred, Y stands for Si and the mixture according tostep (1) further comprises at least one source for X₂O₃ wherein X is Al,and wherein the SiO₂:Al₂O₃ molar ratio of the mixture according to step(1) ranges from 20 to 55, preferably from 25 to 50, and more preferablyfrom 35 to 45. Furthermore, according to said particularly preferredembodiment, the mixture further comprises at least one source forhydroxide anions, preferably a metal hydroxide, more preferably ahydroxide of an alkali metal M, and even more preferably sodiumhydroxide, wherein the OH⁻:SiO₂ molar ratio of the mixture preferablyranges from 0.3 to 0.7, more preferably from 0.4 to 0.65, and even morepreferably from 0.43 to 0.62. In addition to this, the mixture accordingto said particularly preferred embodiment comprises at least one elementsuitable for isomorphous substitution of a least a portion of the Siand/or Al atoms in the BEA framework structure, wherein at least oneelement is preferably selected from the group consisting of Cu, Co, Cr,Ni, Fe, V, and Nb, more preferably from the group consisting of Cu andFe, wherein even more preferably at least one element is Fe.Furthermore, the mixture according to step (1) of said particularlypreferred embodiment further comprises a solvent which is preferablydistilled water, and the mixture of step (1) is crystallized underhydrothermal conditions in step (2) at a temperature ranging from 120 to160° C., more preferably from 130 to 150° C., and even more preferablyfrom 135 to 145° C., and said heating is conducted for a durationranging from 35 to 65 h, more preferably from 40 to 60 h, and even morepreferably from 45 to 55 h. Further preferred according to saidembodiment is an H₂O:SiO₂ molar in the mixture of step (1) of from 15 to45, more preferably from 20 to 40, and even more preferably from 25 to35, and/or an amount of seed crystals ranging from 3 to 20 wt.-%, andmore preferably from 5 to 15 wt.-%.

According to yet a further embodiment of the inventive process which isparticularly preferred, Y stands for Si and the at least one source forSiO₂ is an alkali metal silicate, preferably water glass, morepreferably sodium silicate, wherein the mixture according to step (1)further comprises at least one source for X₂O₃ wherein X is Al, andwherein the SiO₂:Al₂O₃ molar ratio of the mixture according to step (1)ranges from 15 to 40, more preferably from 20 to 35, and even morepreferably from 25 to 30. Furthermore, according to said particularlypreferred embodiment, the mixture further comprises a solvent which ispreferably distilled water, and the mixture of step (1) is crystallizedunder hydrothermal conditions in step (2) at a temperature ranging from120 to 160° C., more preferably from 130 to 150° C., and even morepreferably from 135 to 145° C., and said heating is conducted for aduration ranging from 10 to 16.5 h, more preferably from 12 to 16 h, andeven more preferably from 14 to 15.5 h. Further preferred according tosaid embodiment is an H₂O:SiO₂ molar of 10 to 30, more preferably from15 to 25, and/or an amount of seed crystals ranging from 20 to 40 wt.-%,and even more preferably from 25 to 35 wt.-%. In said particularlypreferred embodiment, the mixture according to step (1) is preferablyagitated during the crystallization in step (2), preferably by rotationof the vessel and/or stirring, and more preferably by stirring themixture.

In general, the process of the present invention can optionally comprisefurther steps for the work-up and/or further physical and/or chemicaltransformation of the zeolitic material having a BEA framework structurecrystallized in step (2) from the mixture provided in step (1). Thecrystallized material can for example be subject to any sequence ofisolation and/or washing procedures, wherein the zeolitic materialobtained from crystallization in step (2) is preferably subject to atleast one isolation and at least one washing procedure.

Isolation of the crystallized product can be achieved by any conceivablemeans. Preferably, isolation of the crystallized product can be achievedby means of filtration, ultrafiltration, diafiltration, centrifugationand/or decantation methods, wherein filtration methods can involvesuction and/or pressure filtration steps.

With respect to one or more optional washing procedures, any conceivablesolvent can be used. Washing agents which may be used are for example,water, alcohols, such as methanol, ethanol or propanol, or mixtures oftwo or more thereof. Examples of mixtures are mixtures of two or morealcohols, such as methanol and ethanol or methanol and propanol orethanol and propanol or methanol and ethanol and propanol, or mixturesof water and at least one alcohol, such as water and methanol or waterand ethanol or water and propanol or water and methanol and ethanol orwater and methanol and propanol or water and ethanol and propanol orwater and methanol and ethanol and propanol. Water or a mixture of waterand at least one alcohol, preferably water and ethanol, is preferred,distilled water being very particularly preferred as the only washingagent.

Preferably, the separated zeolitic material is washed until the pH ofthe washing agent, preferably the washwater, is in the range of from 6to 8, preferably from 6.5 to 7.5, as determined via a standard glasselectrode.

Furthermore, the inventive process can optionally comprise one or moredrying steps. In general, any conceivable means of drying can be used.Drying procedures preferably include heating and/or applying vacuum tothe zeolitic material having a BEA framework structure. In envisagedembodiments of the present invention, one or more drying steps mayinvolve spray drying, preferably spray granulation of the zeoliticmaterial.

In embodiments which comprise at least one drying step, the dryingtemperatures are preferably in the range of from 25° C. to 150° C., morepreferably of from 60 to 140° C., more preferably of from 70 to 130° C.and even more preferably in the range of from 75 to 125° C. Thedurations of drying are preferably in the range of from 2 to 60 h, morepreferably in the range of 6 to 48 hours, and even more preferably offrom 12 to 24 h.

According to the inventive process, the zeolitic material crystallizedin step (2) can optionally be subject to at least one step of anion-exchange procedure, wherein the term “ion-exchange” according to thepresent invention generally refers to non-framework ionic elementsand/or molecules contained in the zeolitic material. In general, anyconceivable ion-exchange procedure with all possible ionic elementsand/or molecules can be conducted on the zeolitic material, with theexception of organic structure directing agents specifically used in thesynthesis of zeolitic materials having a BEA framework structure, inparticular specific tetraalkylammonium salts and/or relatedorganotemplates such as tetraethylammonium and/or dibenzylmethylammoniumsalts and/or dibenzyl-1,4-diazabicyclo[2,2,2]octane. Preferably, asionic elements at least one cation and/or cationic element is employedwhich is preferably selected from the group consisting of H⁺, NH₄ ⁺, Ru,Rh, Pd, Ag, Os, Ir, Pt, Au, more preferably from the group consisting ofPd, Ag, and Pt, and even more preferably from the group consisting of Ptand Pd. Preferably, the zeolitic material is first ion-exchanged with H⁺and/or NH₄ ⁺, and more preferably with NH₄ ⁺, before being subject to afurther ion-exchange procedure, more preferably before being subject toion-exchange with one or more noble metals (Ru, Rh, Pd, Ag, Os, Ir, Pt,Au), more preferably with one or more noble metals selected from thegroup consisting of Pd, Ag, and Pt, and even more preferably with atleast one element selected from Pt and Pd. According to the inventiveprocess it is also preferred that instead of or in addition to saidpreferred ionic elements, the zeolitic material is ion-exchanged withone or more cationic elements selected from the group of elementsconsisting of Cu, Co, Cr, Ni, Fe, V, and Nb.

In general, the optional washing and/or isolation and/or ion-exchangeprocedures comprised in the inventive process can be conducted in anyconceivably order and repeated as often as desired.

Therefore, the process according to the present invention optionallycomprises at least one of the following steps of

(3) isolating the zeolitic material having a BEA framework structure,preferably by filtration, and/or

(4) washing the zeolitic material having a BEA framework structure,and/or

(5) drying the zeolitic material having a BEA framework structure,and/or

(6) subjecting the zeolitic material having a BEA framework structure toan ion-exchange procedure,

wherein the steps (3) and/or (4) and/or (5) and/or (6) can be conductedin any order, and wherein at least one of said steps is preferablyrepeated at least once.

Preferably, the inventive process comprises at least one step ofisolating the zeolitic material crystallized according to step (2), morepreferably by filtration thereof. According to the inventive process itis further preferred that after the at least one step of isolating, thezeolitic material is subject to at least one step of drying, whereinmore preferably the zeolitic material is subject to at least one step ofwashing prior to the at least one drying step. In a particularlypreferred embodiment, the zeolitic material crystallized according tostep (2) is subject to at least one step of isolating, followed by atleast one step of washing, followed by at least one step of drying.

According to a further embodiment of the inventive process, the zeoliticmaterial crystallized in step (2) is directly subject to at least onestep of drying, preferably to spray drying and or spray granulation,without isolating, washing, or drying of the zeolitic materialbeforehand. Directly subjecting the mixture obtained from step (2) ofthe inventive process to a spray drying or spray granulation stage hasthe advantage that isolation and drying is performed in a single stage.Consequently, according to this embodiment of the present invention, aneven more preferred process is provided wherein not only removal oforganotemplate compounds is avoided, but also the number ofpost-synthesis workup steps is minimized, as a result of which theorganotemplate-free zeolitic material having a BEA framework structurecan be obtained from a highly simplified process.

According to a further embodiment of the present invention, the zeoliticmaterial obtained from crystallization in step (2) is subject to atleast one isolating step prior to being subject to at least oneion-exchange procedure, preferably to at least one isolating stepfollowed by at least one washing step, and more preferably to at leastone isolating step followed by at least one washing step followed by atleast one drying step.

The process according to the present invention preferably does notcomprise a calcination step generally involving the heating of thezeolitic material crystallized according to step (2) above a temperatureof 500° C. More preferably, a process according to the present inventionfor the production of a zeolitic material having a BEA frameworkstructure which does not comprise a calcination step refers toprocesses, wherein the zeolitic material crystallized according to step(2) is not subject to a temperature exceeding 450° C., more preferably350° C., more preferably 300° C., more preferably 250° C., morepreferably 200° C., and even more preferably 150° C. According to thepresent invention it is particularly preferred that after completion ofstep (2) of the inventive process, wherein the crystallized zeoliticmaterial is at ambient temperature, said material is subsequently notsubject to any heating process normally or suitably conducted forremoval of organotemplates form a zeolitic material having a BEAframework structure.

The present invention furthermore relates to an organotemplate-freezeolitic material having a BEA framework structure which is eitherobtained by the process according to the present invention or by anyconceivable process which leads to a zeolitic material having a BEAframework structure as obtainable according to the inventive process.

Therefore, the present invention also relates to an organotemplate-freezeolitic material having a BEA framework structure obtainable and/orobtained according to the inventive process.

The present invention, however, also relates to an organotemplate-freezeolitic material having a BEA framework structure having an X-raydiffraction pattern comprising at least the following reflections:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.07-21.27] 100 [22.12-22.32] [14-34] [25.01-25.21] [12-32][26.78-26.98] [14-34] [28.39-28.59] [28-48] [29.24-29.44] [10-30][30.00-30.20] [11-31] [32.86-33.26] [13-33] [42.90-43.30]wherein 100% relates to the intensity of the maximum peak in the X-raypowder diffraction pattern,wherein the BEA framework structure comprises YO₂, and wherein Y is atetravalent element. Preferably, the organotemplate-free zeoliticmaterial having a BEA framework structure has an X-ray diffractionpattern comprising at least the following reflections:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.12-21.22] 100 [22.17-22.27] [14-34] [25.06-25.16] [12-32][26.83-26.93] [14-34] [28.44-28.54] [28-48] [29.29-29.39] [10-30][30.05-30.15] [11-31] [33.01-33.11] [13-33] [43.05-43.15]wherein 100% relates to the intensity of the maximum peak in the X-raypowder diffraction pattern.

According to a preferred embodiment, the organotemplate-free zeoliticmaterial of the present invention has an X-ray diffraction patterncomprising at least the following reflections:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.07-21.27] 100 [22.12-22.32] [14-34] [25.01-25.21] [11-31][25.53-25.73] [12-32] [26.78-26.98] [14-34] [28.39-28.59] [28-48][29.24-29.44] [10-30] [30.00-30.20] [11-31] [32.86-33.26] [13-33][42.90-43.30]wherein more preferably the X-ray diffraction pattern comprises at leastthe following reflections:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.12-21.22] 100 [22.17-22.27] [14-34] [25.06-25.16] [11-31][25.58-25.68] [12-32] [26.83-26.93] [14-34] [28.44-28.54] [28-48][29.29-29.39] [10-30] [30.05-30.15] [11-31] [33.01-33.11] [13-33][43.05-43.15]wherein 100% relates to the intensity of the maximum peak in the X-raypowder diffraction pattern.

Preferably, the organotemplate-free zeolitic material having a BEAframework structure displaying a powder diffraction pattern according tothe present invention is an organotemplate-free zeolitic material whichis either obtained by the process according to the present invention orby any conceivable process which leads to a zeolitic material having aBEA framework structure as obtainable according to the inventiveprocess.

According to the present invention, the zeolitic material does notcontain more than an impurity of an organic structure directing agentspecifically used in the synthesis of zeolitic materials having a BEAframework structure, in particular specific tetraalkylammonium saltsand/or related organotemplates such as tetraethylammonium and/ordibenzylmethylammonium salts, anddibenzyl-1,4-diazabicyclo[2,2,2]octane. Such an impurity can, forexample, be caused by organic structure directing agents still presentin seed crystals used in the inventive process.

According to the present invention, in the zeolitic material having aBEA framework structure, Y stands for any conceivable tetravalentelement, Y standing for either one or several tetravalent elements.Preferred tetravalent elements according to the present inventioninclude Si, Sn, Ti, Zr, and Ge, and combinations thereof. Morepreferably, Y stands for Si, Ti, or Zr, or any combination of saidtrivalent elements, even more preferably for Si and/or Sn. According tothe present invention, it is particularly preferred that Y stands forSi.

In preferred embodiments of the present invention, the framework of thezeolitic material having a BEA structure further comprises X₂O₃, whereinX stands for any conceivable trivalent element, X standing for eitherone or several trivalent elements. Preferred trivalent elementsaccording to the present invention include Al, B, In, and Ga, andcombinations thereof. More preferably, Y stands for Al, B, or In, or anycombination of said trivalent elements, even more preferably for Aland/or B. According to the present invention, it is particularlypreferred that X stands for Al.

Preferably, the zeolitic material of the present invention comprises atleast on alkali metal M, more preferably sodium and/or potassium, andeven more preferably sodium, wherein said at least one alkali metal is anon-framework element of the zeolitic material.

According to the present invention, the organotemplate-free zeoliticmaterial having a BEA framework is preferably non-calcinated, morepreferably within the meaning of the present invention. Even morepreferably, with the exception of the conditions in which it iscrystallized, the zeolitic material having a BEA framework structureaccording to the present invention has not been subject to a heatingprocess normally or suitably conducted for removal of organotemplatesform a zeolitic material having a BEA framework structure.

In preferred embodiments of the present invention, the YO₂:X₂O₃ molarratio of the organotemplate-free zeolitic material ranges from 2 to 100,more preferably from 4 to 70, more preferably from 5 to 50, morepreferably from 6 to 30, more preferably from 7 to 20, more preferablyfrom 8 to 15, and even more preferably from 9 to 13.

It is further preferred according to the present invention that theYO₂:X₂O₃ molar ratio of the organotemplate-free zeolitic material rangesfrom 3 to 20, more preferably from 4 to 18, more preferably from 6 to16, more preferably from 8 to 14, more preferably from 9 to 13, and evenmore preferably from 10.5 to 12.5.

According to preferred embodiments of the present invention, wherein theorganotemplate-free zeolitic material comprises one or more alkalimetals M as non-framework elements, the molar ratio M:X₂O₃ preferablyranges from 0.005 to 10, more preferably from 0.05 to 7, more preferablyfrom 0.5 to 6, more preferably from 1 to 5, more preferably from 1.5 to4.5, and even more preferably from 2 to 4.

According to the present invention it is further preferred that when theorganotemplate-free zeolitic material comprises one or more alkalimetals M as non-framework elements, the molar ratio M:X₂O₃ preferablyranges from 0.001 to 2, more preferably from 0.01 to 1, more preferablyfrom 0.05 to 0.5, more preferably from 0.07 to 0.3, and even morepreferably from 0.1 to 0.2.

In general, at least a portion of the alkali metals optionally presentas non-framework elements in the zeolitic material having a BEAframework structure can be substituted by at least one cation and/orcationic element suited for ion-exchange in the zeolitic material, withthe exception of organic structure directing agents specifically used inthe synthesis of zeolitic materials having a BEA framework structure, inparticular specific tetraalkylammonium salts and/or relatedorganotemplates such as tetraethylammonium and/or dibenzylmethylammoniumsalts and/or dibenzyl-1,4-diazabicyclo[2,2,2]octane. Preferably, atleast one cation and/or cationic element is selected from the groupconsisting of NH₄ ⁺, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, more preferablyfrom the group consisting of Pd, Ag, and Pt, and even more preferablyfrom the group consisting of Pt and Pd. According to the presentinvention it is also preferred that instead of or in addition to saidpreferred ionic elements, one or more cationic element is selected fromthe group of elements consisting of Cu, Co, Cr, Ni, Fe, V, and Nb.

According to preferred embodiments of the present invention, at least aportion of the Y atoms in the BEA framework is isomorphously substitutedby at least one element. In general, Y can be isomorphously substitutedby any suitable element, wherein the at least one element is preferablyselected from the group consisting of Cu, Co, Cr, Ni, Fe, V, and Nb,more preferably from the group consisting of Cu, Co, Cr, Ni, Fe, morepreferably from the group consisting of Cu and Fe, wherein even morepreferably the at least one element is Fe. In a particularly preferredembodiment, at least a portion of the Y atoms in the BEA framework isisomorphously substituted by Fe.

In embodiments according to the present invention, wherein at least aportion of the Y atoms in the BEA framework is isomorphously substitutedby at least one element, the molar ratio of YO₂ to the at least oneelement preferably ranges from 5 to 100, more preferably from 10 to 80,more preferably from 20 to 70, and even more preferably from 25 to 65.Further preferred are embodiments wherein the molar ratio of YO₂ to theat least one element ranges from 5 to 60, more preferably from 10 to 50,more preferably from 20 to 40, and even more preferably from 25 to 35.In addition to these, embodiments are preferred wherein the molar ratioof YO₂ to the at least one element preferably ranges from 30 to 85, morepreferably from 35 to 70, more preferably from 40 to 65, and even morepreferably from 45 to 60.

According to the present invention, the organotemplate-free zeoliticmaterial having a BEA framework structure preferably has a BET surfacearea determined according to DIN 66135 of from 200 to 700 m²/g,preferably from 400 to 650 m²/g, more preferably from 475 to 575 m²/g,and even more preferably from 500 to 550 m²/g.

Depending on the specific needs of its application, the inventivematerial can be employed as such, like in the form of a powder, a spraypowder or a spray granulate obtained from above-described separationtechniques, e.g. decantation, filtration, centrifugation, or spraying.

In many industrial applications, it is often desired on the part of theuser not to employ the zeolitic material as powder or sprayed material,i.e. the zeolitic material obtained by the separation of the materialfrom its mother liquor, optionally including washing and drying, andsubsequent calcination, but a zeolitic material which is furtherprocessed to give moldings. Such moldings are required particularly inmany industrial processes, e.g. in many processes wherein the zeoliticmaterial of the present invention is employed as catalyst or adsorbent.

Accordingly, the present invention also relates to a molding comprisingthe zeolitic material of the present invention having a BEA frameworkstructure.

In general, the powder or sprayed material can be shaped without anyother compounds, e.g. by suitable compacting, to obtain moldings of adesired geometry, e.g. tablets, cylinders, spheres, or the like.

Preferably, the powder or sprayed material is admixed with or coated bya suitable refractory binder. In general, suitable binders are allcompounds which impart adhesion and/or cohesion between the zeoliticmaterial particles to be bonded which goes beyond the physisorptionwhich may be present without a binder. Examples of such binders aremetal oxides, such as, for example, SiO₂, Al₂O₃, TiO₂, ZrO₂ or MgO orclays, or mixtures of two or more of these compounds. Naturallyoccurring clays which can be employed include the montmorillonite andkaolin family, which families include the subbentonites, and the kaolinscommonly known as Dixie, McNamee, Georgia and Florida clays or others inwhich the main mineral constituent is halloysite, kaolinite, dickite,nacrite, or anauxite. Such clays can be used in the raw state asoriginally mined or initially subjected to calcination, acid treatmentor chemical modification. In addition, the zeolitic material accordingto the present invention can be composited with a porous matrix materialsuch as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria,silica-beryllia and silica-titania as well as ternary compositions suchas silica-alumina-thoria, silica-alumina-zirconia,silica-alumina-magnesia and silica-magnesia-zirconia.

Also preferably, the powder or the sprayed material, optionally afteradmixing or coating by a suitable refractory binder as described above,is formed into a slurry, for example with water, which is deposited upona suitable refractory carrier. The slurry may also comprise othercompounds such as, e.g., stabilizers, defoamers, promoters, or the like.Typically, the carrier comprises a member, often referred to as a“honeycomb” carrier, comprising one or more refractory bodies having aplurality of fine, parallel gas flow passages extending therethrough.Such carriers are well known in the art and may be made of any suitablematerial such as cordierite or the like.

In general, the zeolitic material described above can be used asmolecular sieve, adsorbent, catalyst, catalyst support or binderthereof. Especially preferred is the use as catalyst. For example, thezeolitic material can be used as molecular sieve to dry gases orliquids, for selective molecular separation, e.g. for the separation ofhydrocarbons or amides; as ion exchanger; as chemical carrier; asadsorbent, in particular as adsorbent for the separation of hydrocarbonsor amides; or as a catalyst. Most preferably, the zeolitic materialaccording to the present invention is used as a catalyst.

According to a preferred embodiment of the present invention, theorganotemplate-free zeolitic material of the invention is used in acatalytic process, preferably as a catalyst and/or catalyst support, andmore preferably as a catalyst. In general, the zeolitic material of theinvention can be used as a catalyst and/or catalyst support in anyconceivable catalytic process, wherein processes involving theconversion of at least one organic compound is preferred, morepreferably of organic compounds comprising at least one carbon-carbonand/or carbon-oxygen and/or carbon-nitrogen bond, more preferably oforganic compounds comprising at least one carbon-carbon and/orcarbon-oxygen bond, and even more preferably of organic compoundscomprising at least one carbon-carbon bond. In particularly preferredembodiments of the present invention, the zeolitic material is used as acatalyst and/or catalyst support in a fluid catalytic cracking (FCC)process. According to a further embodiment of the present invention, thezeolitic material of the invention is preferably used in a catalyticprocess involving the conversion of at least one compound comprising atleast one nitrogen-oxygen bond.

Particularly preferred according to the present invention is the use ofthe zeolitic material having a BEA framework structure as a catalystand/or catalyst support in a selective catalytic reduction (SCR) processfor the selective reduction of nitrogen oxides NO_(x); for the oxidationof NH₃, in particular for the oxidation of NH₃ slip in diesel systems;for the decomposition of N₂O; for soot oxidation; for emission controlin Advanced Emission Systems such as Homogeneous Charge CompressionIgnition (HCCI) engines; as additive in fluid catalytic cracking (FCC)processes; as catalyst in organic conversion reactions; or as catalystin “stationary source” processes.

The term nitrogen oxides, NO_(x), as used in the context of the presentinvention designates the oxides of nitrogen, especially dinitrogen oxide(N₂O), nitrogen monoxide (NO), dinitrogen trioxide (N₂O₃), nitrogendioxide (NO₂), dinitrogen tetroxide (N₂O₄), dinitrogen pentoxide (N₂O₅),nitrogen peroxide (NO₃).

Therefore, the present invention also relates to a method forselectively reducing nitrogen oxides NO_(x) by contacting a streamcontaining NO_(x) with a catalyst containing the zeolitic materialhaving a BEA framework structure according to the present inventionunder suitable reducing conditions; to a method of oxidizing NH₃, inparticular of oxidizing NH₃ slip in diesel systems, by contacting astream containing NH₃ with a catalyst containing the zeolitic materialhaving a BEA framework structure according to the present inventionunder suitable oxidizing conditions; to a method of decomposing of N₂Oby contacting a stream containing N₂O with a catalyst containing thezeolitic material having a BEA framework structure according to thepresent invention under suitable decomposition conditions; to a methodof controlling emissions in Advanced Emission Systems such asHomogeneous Charge Compression Ignition (HCCI) engines by contacting anemission stream with a catalyst containing the zeolitic material havinga BEA framework structure according to the present invention undersuitable conditions; to a fluid catalytic cracking FCC process whereinthe zeolitic material having a BEA framework structure according to thepresent invention is employed as additive; to a method of converting anorganic compound by contacting said compound with a catalyst containingthe zeolitic material having a BEA framework structure according to thepresent invention under suitable conversion conditions; to a “stationarysource” process wherein a catalyst is employed containing the zeoliticmaterial having a BEA framework structure according to the presentinvention.

Therefore, the present invention also relates to a method forselectively reducing nitrogen oxides NO_(x), wherein a gaseous streamcontaining nitrogen oxides NO_(x), preferably also containing ammoniaand/urea, is contacted with the zeolitic material according to thepresent invention or the zeolitic material obtainable of obtainedaccording to the present invention, preferably in the form of a moldedcatalyst, still more preferably as a molded catalyst wherein thezeolitic material is deposited on a suitable refractory carrier, stillmore preferably on a “honeycomb” carrier.

The nitrogen oxides which are reduced using a catalyst containing thezeolitic material according to the present invention or the zeoliticmaterial obtainable of obtained according to the present invention maybe obtained by any process, e.g. as a waste gas stream. Among others,waste gas streams as obtained in processes for producing adipic acid,nitric acid, hydroxylamine derivatives, caprolactame, glyoxal,methyl-glyoxal, glyoxylic acid or in processes for burning nitrogenousmaterials may be mentioned.

Most preferably, the zeolitic material according to the presentinvention or the zeolitic material obtainable of obtained according tothe present invention is used as a molded catalyst, still morepreferably as a molded catalyst wherein the zeolitic material isdeposited on a suitable refractory carrier, still more preferably on a“honeycomb” carrier, for the selective reduction of nitrogen oxidesNO_(x), i.e. for selective catalytic reduction of nitrogen oxides. Inparticular, the selective reduction of nitrogen oxides wherein thezeolitic material according to the present invention is employed ascatalytically active material is carried out in the presence ammonia orurea. While ammonia is the reducing agent of choice for stationary powerplants, urea is the reducing agent of choice for mobile SCR systems.Typically, the SCR system is integrated in the engine and vehicle designand, also typically, contains the following main components: SCRcatalyst containing the zeolitic material according to the presentinvention; a urea storage tank; a urea pump; a urea dosing system; aurea injector/nozzle; and a respective control unit.

When preparing specific catalytic compositions or compositions fordifferent purposes, it is also conceivable to blend the zeoliticmaterial according to the present invention having a BEA frameworkstructure with at least one other catalytically active material or amaterial being active with respect to the intended purpose. It is alsopossible to blend at least two different inventive materials which maydiffer in the YO₂:X₂O₃ ratio, preferably in the SiO₂:Al₂O₃ ratio, and/orin the presence or absence of a further metal such as a transition metaland/or in the specific amounts of a further metal such as a transitionmetal. It is also possible to blend at least two different inventivematerials with at least one other catalytically active material or amaterial being active with respect to the intended purpose.

The catalysts of the present invention may also be provided in the formof extrudates, pellets, tablets or particles of any other suitableshape, for use as a packed bed of particulate catalyst, or as shapedpieces such as plates, saddles, tubes, or the like.

Also, the catalyst may be disposed on a substrate. The substrate may beany of those materials typically used for preparing catalysts, and willusually comprise a ceramic or metal honeycomb structure. Any suitablesubstrate may be employed, such as a monolithic substrate of the typehaving fine, parallel gas flow passages extending therethrough from aninlet or an outlet face of the substrate, such that passages are open tofluid flow therethrough (referred to as honeycomb flow throughsubstrates). The passages, which are essentially straight paths fromtheir fluid inlet to their fluid outlet, are defined by walls on whichthe catalytic material is disposed as a washcoat so that the gasesflowing through the passages contact the catalytic material. The flowpassages of the monolithic substrate are thin-walled channels, which canbe of any suitable cross-sectional shape and size such as trapezoidal,rectangular, square, sinusoidal, hexagonal, oval, circular, etc. Suchstructures may contain from about 60 to about 400 or more gas inletopenings (i.e., cells) per square inch (2.54 cm×2.54 cm) of crosssection.

The substrate can also be a wall-flow filter substrate, where thechannels are alternately blocked, allowing a gaseous stream entering thechannels from one direction (inlet direction), to flow through thechannel walls and exit from the channels from the other direction(outlet direction). The catalyst composition can be coated on the flowthrough or wall-flow filter. If a wall flow substrate is utilized, theresulting system will be able to remove particulate matter along withgaseous pollutants. The wall-flow filter substrate can be made frommaterials commonly known in the art, such as cordierite, aluminumtitanate or silicon carbide. It will be understood that the loading ofthe catalytic composition on a wall flow substrate will depend onsubstrate properties such as porosity and wall thickness, and typicallywill be lower than loading on a flow through substrate.

The ceramic substrate may be made of any suitable refractory material,e.g., cordierite, cordierite-alumina, silicon nitride, zircon mullite,spodumene, alumina-silica magnesia, zircon silicate, sillimanite, amagnesium silicate, zircon, petalite, alpha-alumina, an aluminosilicate,and the like.

The substrates useful for the catalysts of embodiments of the presentinvention may also be metallic in nature and be composed of one or moremetals or metal alloys. The metallic substrates may be employed invarious shapes such as corrugated sheet or monolithic form. Suitablemetallic supports include the heat resistant metals and metal alloyssuch as titanium and stainless steel as well as other alloys in whichiron is a substantial or major component. Such alloys may contain one ormore of nickel, chromium and/or aluminum, and the total amount of thesemetals may advantageously comprise at least 15 wt. % of the alloy, e.g.,10-25 wt. % of chromium, 3-8 wt. % of aluminum and up to 20 wt. % ofnickel. The alloys may also contain small or trace amounts of one ormore other metals such as manganese, copper, vanadium, titanium, and thelike. The surface or the metal substrates may be oxidized at hightemperatures, e.g., 1000° C. and higher, to improve the resistance tocorrosion of the alloys by forming an oxide layer on the surfaces of thesubstrates. Such high temperature-induced oxidation may enhance theadherence of the refractory metal oxide support and catalyticallypromoting metal components to the substrate.

In alternative embodiments, zeolitic material according to the presentinvention having a BEA framework structure may be deposited on an opencell foam substrate. Such substrates are well known in the art, and aretypically formed of refractory ceramic or metallic materials.

Especially preferred is the use of a catalyst containing the zeoliticmaterial according to the present invention or the zeolitic materialobtainable or obtained according to the present invention for removal ofnitrogen oxides NO_(x) from exhaust gases of internal combustionengines, in particular diesel engines, which operate at combustionconditions with air in excess of that required for stoichiometriccombustion, i.e., lean.

Therefore, the present invention also relates to a method for removingnitrogen oxides NO_(x) from exhaust gases of internal combustionengines, in particular diesel engines, which operate at combustionconditions with air in excess of that required for stoichiometriccombustion, i.e., at lean conditions, wherein a catalyst containing thezeolitic material according to the present invention or the zeoliticmaterial obtainable or obtained according to the present invention isemployed as catalytically active material.

The present invention therefore relates to the use of theorganotemplate-free zeolitic material of the invention, in particular inthe field of catalysis and/or in the treatment of exhaust gas, whereinsaid exhaust gas treatment comprises industrial and automotive exhaustgas treatment. In these and other applications, the zeolitic material ofthe present invention can by way of example be used as a molecularsieve, catalyst, and/or catalyst support.

In embodiments of the present invention involving the use of thezeolitic material of the invention in exhaust gas treatment, thezeolitic material is preferably used in the treatment of industrial orautomotive exhaust gas, more preferably as a molecular sieve in saidapplications. In a particularly preferred embodiment, the zeoliticmaterial used in exhaust gas treatment is comprised in a hydrocarbontrap.

The present invention moreover relates to methods for the use of theorganotemplate-free zeolitic material of the invention, in particular inthe field of catalysis and/or in the treatment of exhaust gas, whereinsaid exhaust gas treatment comprises industrial and automotive exhaustgas treatment. In these and other methods of use, the zeolitic materialof the present invention can by way of example be used as a molecularsieve, catalyst, and/or catalyst support.

According to a preferred embodiment of the present invention, the methodinvolves the use of the organotemplate-free zeolitic material of theinvention in a catalytic process, preferably as a catalyst and/orcatalyst support, and more preferably as a catalyst. In general, in themethods according to the present invention the zeolitic material of theinvention can be used as a catalyst and/or catalyst support in anyconceivable catalytic process, wherein processes involving theconversion of at least one organic compound is preferred, morepreferably of organic compounds comprising at least one carbon-carbonand/or carbon-oxygen and/or carbon-nitrogen bond, more preferably oforganic compounds comprising at least one carbon-carbon and/orcarbon-oxygen bond, and even more preferably of organic compoundscomprising at least one carbon-carbon bond. In particularly preferredembodiments of the present invention, in said methods of use thezeolitic material is used as a catalyst and/or catalyst support in afluid catalytic cracking (FCC) process.

According to a further embodiment of the present invention, the methodof use involves the use of the zeolitic material of the invention in acatalytic process involving the conversion of at least one compoundcomprising at least one nitrogen-oxygen bond. Particularly preferred aremethods of use wherein the zeolitic material of the invention is used asa catalyst and/or catalyst support in a selective catalytic reduction(SCR) process.

In embodiments of the present invention involving a method of use of thezeolitic material of the invention in exhaust gas treatment, thezeolitic material is preferably used in the treatment of industrial orautomotive exhaust gas, more preferably as a molecular sieve in saidapplications. In a particularly preferred embodiment, in the method ofuse for exhaust gas treatment the zeolitic material of the invention iscomprised in a hydrocarbon trap.

In addition to the above-mentioned, the present invention furthercomprises the following embodiments:

-   1. An organotemplate-free synthetic process for the production of a    zeolitic material having a BEA framework structure comprising YO₂    and optionally comprising X₂O₃, wherein said process comprises the    steps of    -   (1) preparing a mixture comprising seed crystals and at least        one source for YO₂; and    -   (2) crystallizing the mixture,    -   wherein Y is a tetravalent element, and X is a trivalent        element,    -   wherein the zeolitic material optionally comprises at least one        alkali metal M,    -   wherein when the BEA framework additionally comprises X₂O₃, the        mixture according to step (1) comprises at least one source for        X₂O₃, and    -   wherein the seed crystals comprise zeolitic material having a        BEA framework structure, preferably zeolite Beta.-   2. The process according to embodiment 1, wherein Y is selected from    the group consisting of Si, Sn, Ti, Zr, Ge, and a mixture of two or    more thereof, Y preferably being Si.-   3. The process according to embodiment 1 or 2, wherein the at least    one source for YO₂ comprises at least one silicate, preferably a    silicate of an alkali metal M.-   4. The process according to embodiment 3, wherein the at least one    source for YO₂ comprises water glass, preferably sodium and/or    potassium silicate, more preferably sodium silicate.-   5. The process according to any one of embodiments 1 to 4, wherein X    is selected from the group consisting of Al, B, In, Ga, and a    mixture of two or more thereof, X preferably being Al.-   6. The process according to any one of embodiments 1 to 5, wherein    the at least one source for X₂O₃ comprises at least one aluminate    salt, preferably an aluminate of an alkali metal M.-   7. The process according to embodiment 6, wherein the at least one    source for X₂O₃ comprises sodium and/or potassium aluminate,    preferably sodium aluminate.-   8. The process according to any one of embodiments 1 to 7, wherein    the YO₂:X₂O₃ molar ratio of the mixture according to step (1) ranges    from 20 to 55.-   9. The process according to any one, of embodiments 1 to 8, wherein    the amount of seed crystals in the mixture according to step (1)    ranges from 1 to 35 wt.-% based on 100 wt.-% of YO₂ in the at least    one source for YO₂.-   10. The process according to any one of embodiments 1 to 9, wherein    the mixture according to step (1) further comprises a solvent,    wherein said solvent preferably comprises water.-   11. The process according to embodiment 10, wherein the H₂O:YO₂    molar ratio of the mixture according to step (1) ranges from 7 to    45.-   12. The process according to any one of embodiments 1 to 11, wherein    the mixture according to step (1) further comprises at least one    source for OH⁻, wherein said at least one source for OH⁻ preferably    comprises a metal hydroxide, more preferably a hydroxide of an    alkali metal M, even more preferably sodium and/or potassium    hydroxide.-   13. The process according to embodiment 12, wherein the OH⁻:YO₂    molar ratio of the mixture according to step (1) ranges from 0.3 to    0.7.-   14. The process according to any one of embodiments 1 to 13, wherein    the mixture according to step (1) further comprises at least one    source of at least one element suitable for isomorphous substitution    of at least a portion of the Y atoms, and/or of the X atoms in the    BEA framework structure, wherein at least one element is preferably    selected from the group consisting of Cu, Co, Cr, Ni, Fe, V, and Nb,    and wherein more preferably at least one element is Fe.-   15. The process according to embodiment 14, wherein the molar ratio    of YO₂ to the at least one element suitable for isomorphous    substitution of at least a portion of the Y atoms and/or of the X    atoms in the BEA framework structure ranges from 40 to 100.-   16. The process according to any one of embodiments 1 to 15, wherein    the M:YO₂ molar ratio in the mixture according to step (1) ranges    from of 0.2 to 1.-   17. The process according to any one of embodiments 1 to 16, wherein    the YO₂:X₂O₃:M molar ratios in the mixture according to step (1)    range from (20-55):1:(11-40).-   18. The process according to any one of embodiments 1 to 17, wherein    the crystallization in step (2) involves heating of the mixture,    preferably at a temperature ranging from 100 to 160° C.-   19. The process according to any one of embodiments 18, wherein the    crystallization in step (2) is conducted under solvothermal    conditions.-   20. The process according to embodiment 18 or 19, wherein the    crystallization in step (2) involves heating of the mixture for a    period ranging from 10 to 16.5 h.-   21. The process according to any one of embodiments 1 to 20, wherein    the crystallization in step (2) involves agitating the mixture,    preferably by stirring.-   22. The process according to any one of embodiments 1 to 21 further    comprising at least one of the following steps of    -   (3) isolating the zeolitic material having a BEA framework        structure, preferably by filtration, and/or    -   (4) washing the zeolitic material having a BEA framework        structure, and/or    -   (5) drying the zeolitic material having a BEA framework        structure, and/or    -   (6) subjecting the zeolitic material having a BEA framework        structure to an ion-exchange procedure,    -   wherein the steps (3) and/or (4) and/or (5) and/or (6) can be        conducted in any order, and    -   wherein at least one of said steps is preferably repeated at        least once.-   23. The process according to embodiment 22, wherein in the at least    one step (6) at least one ionic non-framework element contained in    the zeolitic material having a BEA framework is ion-exchanged,    preferably against at least one cation and/or cationic element,    wherein at least one cation and/or cationic element is preferably    selected from the group consisting of H⁺, NH₄ ⁺, Ru, Rh, Pd, Ag, Os,    Ir, Pt, Au, more preferably from the group consisting of Pd, Ag, and    Pt, and even more preferably from the group consisting of Pt and Pd.-   24. The process according to any one of embodiments 1 to 23, wherein    the zeolitic material having a BEA framework structure formed in    step (2) comprises zeolite Beta.-   25. The process according to any one of embodiments 1 to 24, wherein    the seed crystals comprise a zeolitic material having a BEA    framework structure as synthesized according to the process of any    one of embodiments 1 to 24, preferably zeolite Beta.-   26. The process according to any one of embodiments 1 to 25, wherein    the organotemplate-free synthesis does not comprise a calcination    step.-   27. An organotemplate-free zeolitic material having a BEA framework    structure obtainable and/or obtained according to any one of    embodiments 1 to 26, wherein said zeolitic material is preferably    non-calcinated.-   28. An organotemplate-free zeolitic material having a BEA framework    structure, optionally obtainable and/or obtained according to any    one of embodiments 1 to 27, having an X-ray diffraction pattern    comprising at least the following reflections:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.07-21.27] 100 [22.12-22.32] [14-34] [25.01-25.21] [12-32][26.78-26.98] [14-34] [28.39-28.59] [28-48] [29.24-29.44] [10-30][30.00-30.20] [11-31] [32.86-33.26] [13-33] [42.90-43.30]

-   -   wherein 100% relates to the intensity of the maximum peak in the        X-ray powder diffraction pattern,    -   wherein the BEA framework structure comprises YO₂ and optionally        comprises X₂O₃,    -   wherein Y is a tetravalent element, and X is a trivalent        element,    -   wherein the zeolitic material optionally comprises at least one        alkali metal M, and    -   wherein the zeolitic material is preferably non-calcinated.

-   29. The organotemplate-free zeolitic material according to    embodiment 28, wherein the X-ray diffraction pattern comprises the    following reflection:

Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [11-31][25.53-25.73]

-   30. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 29, wherein the YO₂:X₂O₃ molar ratio ranges    from 3 to 20.-   31. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 30, wherein the molar ratio of alkali metal    M:X₂O₃ ranges from 1 to 5.-   32. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 31, wherein Y is selected from the group    consisting of Si, Sn, Ti, Zr, Ge, and a mixture of two or more    thereof, Y preferably being Si.-   33. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 32, wherein X is selected from the group    consisting of Al, B, In, Ga, and a mixture of two or more thereof, X    preferably being Al.-   34. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 33, wherein said material comprises at least    sodium and/or potassium, preferably at least sodium.-   35. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 34, wherein at least a portion of the Y atoms    and/or of the X atoms in the BEA framework structure is    isomorphously substituted by at least one element, wherein at least    one element is preferably selected from the group consisting of Cu,    Co, Cr, Ni, Fe, V, and Nb, and wherein more preferably at least one    element is Fe.-   36. The organotemplate-free zeolitic material according to    embodiment 35, wherein the molar ratio of YO₂ to the at least one    element ranges from 20 to 70.-   37. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 36, wherein at least a portion of the alkali    metal atoms M is substituted by at least one cation and/or cationic    element, wherein at least one cation and/or cationic element is    preferably selected from the group consisting of H⁺, NH₄ ⁺, Ru, Rh,    Pd, Ag, Os, Ir, Pt, Au, more preferably from the group consisting of    Pd, Ag, and Pt, and even more preferably from the group consisting    of Pt and Pd.-   38. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 37, wherein the BET surface area of the    zeolitic material determined according to DIN 0.66135 ranges from    400 to 650 m²/g, preferably from 475 to 575 m²/g.-   39. The organotemplate-free zeolitic material according to any one    of embodiments 27 to 38, wherein said material comprises zeolite    Beta.-   40. Use of an organotemplate-free zeolitic material according to any    one of embodiments 27 to 39 in a catalytic process, preferably as a    catalyst.-   41. The use according to embodiment 40 in a fluid catalytic cracking    (FCC) process or in selective catalytic reduction (SCR).-   42. Use of an organotemplate-free zeolitic material according to any    one of embodiments 27 to 39 in exhaust gas treatment, preferably in    the treatment of industrial or automotive exhaust gas.-   43. The use according to embodiment 42 wherein the zeolitic material    is comprised in a hydrocarbon trap.-   44. A method of using an organotemplate-free zeolitic material    according to any one of embodiments 27 to 39 in a catalytic process,    preferably as a catalyst.-   45. The method of claim 44, wherein the organotemplate-free zeolitic    material is used as a catalyst in a fluid catalytic cracking (FCC)    process or in selective catalytic reduction (SCR).-   46. A method of using an organotemplate-free zeolitic material    according to any one of embodiments 27 to 39 in exhaust gas    treatment, preferably in the treatment of industrial or automotive    exhaust gas.-   47. The method of claim 46 wherein the zeolitic material is    comprised in a hydrocarbon trap.

DESCRIPTION OF THE FIGURES

The powder X-ray diffraction patterns displayed in the figures wererecorded on a Siemens D-5000 with monochromatic Cu K alpha-1 radiation,a capillary sample holder being used in order to avoid a preferredorientation. The diffraction data were collected using aposition-sensitive detector from Braun, in the range from 8 to 96° (2theta) and with a step width of 0.0678°. Indexing of the powder diagramwas effected using the program Treor90, implemented in powder-X (Treor90is a public domain program which is freely accessible via the URLhttp://www.ch.iucr.org/sincris-top/logiciel/). In the figure, the angle2 theta in ° is shown along the abscissa and the intensities are plottedalong the ordinate.

FIG. 1a shows the X-ray diffraction (XRD) pattern and scanning electronmicroscope (SEM) image of the Beta seeds supplied from Sinopec CatalystCompany used in the Examples.

FIGS. 1b , 2-10, 11 a, 12, 13 a, 14, and 15 a show the X-ray diffractionpattern of the crystalline material obtained according to Examples 1 to10, 11A, and 12 to 15, respectively. FIG. 14 further includes both theline patterns of zeolite Beta obtained from template mediated synthesisand from mordenite for comparison.

FIG. 11b shows the X-ray diffraction pattern of the crystalline materialobtained from Example 11A together with the line pattern of zeolite Betaobtained from template mediated synthesis.

FIGS. 1c, 11d, 13b and c, and 15b and c show the scanning electronmicroscope (SEM) images obtained from samples of the crystallineproducts obtained according to Examples 1, 11A, 13, and 15,respectively.

FIGS. 1d and 11e show the nitrogen adsorption isotherms according toExamples 1 and 11A, respectively. In these figures, the relativepressure p/p⁰ is plotted along the abscissa and the pore volume in ml/g(STP (standard pressure and temperature)), determined according to DIN66134 at 77 K, is plotted along the ordinate.

FIG. 11c shows the ²⁷Al MAS NMR spectrum of the crystalline materialobtained according to Example 11A.

EXAMPLES Example 1

0.117 g of NaAlO₂ and 0.36 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:10.46 Na₂O:566.66 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 19 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

FIG. 1a shows the XRD and SEM of the zeolite Beta seeds commerciallyobtained from Sinopec Catalyst Company.

In FIG. 1b , the XRD of the crystalline product obtained from theorganotemplate-free synthesis of Example 1 after filtration and dryingis displayed. In particular, the XRD pattern is typical for a BEAframework structure.

FIG. 1c shows an SEM image of the crystalline material obtainedaccording to Example 1.

In FIG. 1d , the nitrogen isotherm obtained using the crystallinematerial from Example 1 is shown. In particular, the step-like curve ofa type I adsorption isotherm typical of microporous solids is evident(cf. DIN 66135), indicating that the as-synthesized zeolitic materialhas open micropores.

Example 2

0.117 g of NaAlO₂ and 0.40 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:11.46 Na₂O:566.66 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 19 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 2, the XRD of the crystalline product obtained according toExample 2 is displayed. As can be seen from the XRD pattern, the producthas a BEA framework structure.

Example 3

0.117 g of NaAlO₂ and 0.45 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:12.72 Na₂O:566.26 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 19 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 3, the XRD of the crystalline product obtained according toExample 3 is displayed.

Example 4

0.15 g of NaAlO₂ and 0.45 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 31.42 SiO₂:1.00 Al₂O₃:10.23 Na₂O:442.57 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 21 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 4, the XRD of the crystalline product obtained according toExample 4 is displayed, showing additional weak reflections stemmingfrom mordenite side-product.

Example 5

0.117 g of NaAlO₂ and 0.40 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:11.46 Na₂O:566.66 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 21 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 5, the XRD of the crystalline product obtained according toExample 5 is displayed, showing additional weak reflections stemmingfrom mordenite side-product.

Example 6

0.15 g of NaAlO₂ and 0.45 g of NaOH were dissolved in 5.04 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 31.42 SiO₂:1.00 Al₂O₃:10.23 Na₂O:442.57 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 24 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 6, the XRD of the crystalline product obtained according toExample 6 is displayed, showing additional weak reflections stemmingfrom mordenite and zeolite P side-products.

Example 7

0.117 g of NaAlO₂ and 0.40 g of NaOH were dissolved in 7.20 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:11.46 Na₂O:809.51 H₂O. 0.12 g of zeoliteBeta seeds (commercially obtained from Sinopec Catalyst Co.) were thenintroduced into the gel, followed by stirring for 15 min at roomtemperature. The gel mixture was then transferred into an autoclave andcrystallized at 140° C. for 19 h. After having let the reaction mixturecool to room temperature, it was filtered and then dried at 80° C., thusaffording a crystalline product.

In FIG. 7, the XRD of the crystalline product obtained according toExample 7 is displayed.

Example 8

0.117 g of NaAlO₂ and 0.456 g of NaOH were dissolved in 10.08 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:13.06 Na₂O:1133.32 H₂O. 0.12 g ofzeolite Beta seeds (commercially obtained from Sinopec Catalyst Co.)were then introduced into the gel, followed by stirring for 15 min atroom temperature. The gel mixture was then transferred into an autoclaveand crystallized at 140° C. for 19 h. After having let the reactionmixture cool to room temperature, it was filtered and then dried at 80°C., thus affording a crystalline product.

In FIG. 8, the XRD of the crystalline product obtained according toExample 8 is displayed.

Example 9

0.117 g of NaAlO₂ and 0.44 g of NaOH were dissolved in 11.52 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40:28 SiO₂:1.00 Al₂O₃:12.61 Na₂O:1295.22 H₂O. 0.12 g ofzeolite Beta seeds (commercially obtained from Sinopec Catalyst Co.)were then introduced into the gel, followed by stirring for 15 min atroom temperature. The gel mixture was then transferred into an autoclaveand crystallized at 140° C. for 19 h. After having let the reactionmixture cool to room temperature, it was filtered and then dried at 80°C., thus affording a crystalline product.

In FIG. 9, the XRD of the crystalline product obtained according toExample 9 is displayed.

Example 10

0.117 g of NaAlO₂ and 0.48 g of NaOH were dissolved in 14.40 ml of H₂O,followed by addition of 1.2 g of fumed silica. The mixture was thenstirred for 15 min, thus affording an aluminosililcate gel with a molarratios of 40.28 SiO₂:1.00 Al₂O₃:13.75 Na₂O:1619.03 H₂O. 0.12 g ofzeolite Beta seeds (commercially obtained from Sinopec Catalyst Co.)were then introduced into the gel, followed by stirring for 15 min atroom temperature. The gel mixture was then transferred into an autoclaveand crystallized at 140° C. for 19 h. After having let the reactionmixture cool to room temperature, it was filtered and then dried at 80°C., thus affording a crystalline product.

In FIG. 10, the XRD of the crystalline product obtained according toExample 10 is displayed.

Example 11A

1.34 g of NaAlO₂ and 6.54 g of NaOH were dissolved in 142.23 ml of H₂Owhile stirring, followed by addition of 1.69 g of zeolite Beta seeds(commercially obtained from Zeolyst International). 16.87 g of fumedsilica (Aerosil® 200) was then added to the mixture in portions whilestirring during 30 min, after which the mixture was stirred for anadditional 30 min, thus affording an aluminosililcate gel with a molarratio of 40.28 SiO₂:1.00 Al₂O₃:13.06 Na₂O:1132.32 H₂O. The gel mixturewas then transferred into a Teflon®-lined autoclave and crystallized at140° C. for 48 h. After having let the reaction mixture cool to roomtemperature, it was filtered, repeatedly washed with distilled water,and then dried at 120° C. for 16 h, thus affording 5.9 g of a whitecrystalline product.

Electron Probe Micro Analysis of the crystalline product of Example 11Avia Energy Dispersive X-Ray Spectroscopy (EDXS) afforded an SiO₂:Al₂O₃molar ratio of 10.1.

In FIG. 11a , the XRD of the crystalline product obtained according toExample 11A is displayed, including the 2 Theta values and respectiveintensities for the individual reflections. Additional weak reflectionsstemming from mordenite side-product are visible in thepowder-diffraction pattern.

In FIG. 11b , the XRD pattern of Example 11A is displayed together withthe line pattern of zeolite Beta as synthesized with an organic templateas the structure directing agent. In particular, it is apparent that thereflections of the zeolitic material obtained by organotemplate-freesynthesis according to the present invention are noticeably shiftedtowards smaller 2 Theta values compared to the reflections of zeoliteBeta obtained using an organic template.

FIG. 11c displays the ²⁷Al MAS NMR obtained for the crystalline finalproduct of Example 11A, displaying a single signal at 53.1 ppm. Thisindicates that the Al is entirely incorporated into the zeoliteframework.

FIG. 11d shows a SEM-image of the crystalline product obtained accordingto Example 11A.

In FIG. 11e , the nitrogen isotherm obtained using the crystallineproduct of Example 11A is shown. In particular, the step-like curve of atype I adsorption isotherm typical of microporous solids is evident (cf.DIN 66135), indicating that the as-synthesized zeolitic material hasopen micropores. The evaluation of the data gave an equivalent surfaceof 684.45 m²/g according to the Langmuir method, and a BET surface areaof 523.08 m²/g.

Example 11B Ion-Exchange

1.34 g of NaAlO₂ and 6.54 g of NaOH were dissolved in 142.23 ml of H₂Owhile stirring, followed by addition of 1.69 g of zeolite Beta seeds(commercially obtained from Zeolyst International). 16.87 g of fumedsilica (Aerosil® 200) was then added to the mixture in portions whilestirring during 30 min, after which the mixture was stirred for anadditional 30 min, thus affording an aluminosililcate gel with a molarratio of 40.28 SiO₂:1.00 Al₂O₃:13.06 Na₂O:1132.32 H₂O. The gel mixturewas then crystallized in an autoclave at 140° C. for 48 h. After havinglet the reaction mixture cool to room temperature, it was filtered,repeatedly washed with distilled water, and then dried at 120° C. for 16h, thus affording 5.7 g of a white crystalline product.

Elemental analysis of the crystalline product of said first crystallineproduct afforded Na:SiO₂:Al₂O₃ molar ratios of 2.8:11.7:1.

4.0 g of the crystalline product were then added to a solution of 4 g ofNH₄NO₃ dissolved in 36 g of distilled water and the mixture was stirredfor 2 h at 80° C. The solid was then filtered and washed with distilledwater, after which the solid was added to a new solution of 4 g ofNH₄NO₃ dissolved in 36 g of distilled water and the mixture then stirredfor 2 h at 80° C. After filtering and washing the solid with distilledwater, the resulting product was then dried for 16 h at 120° C., toafford the ion-exchanged crystalline product.

Elemental analysis of the final crystalline product of Example 11Bafforded an Na:Al₂O₃ molar ratio of 0.13.

Example 12

18.9 g of NaAlO₂ were dissolved in 701 ml of H₂O. 610.9 g ofsodium-water glass and 47.5 g of zeolite Beta seeds (commerciallyobtained from Zeolyst International) were then added, thus affording analuminosililcate gel with a molar ratio of 40.28 SiO₂:1.50 Al₂O₃:14.0Na₂O:936 H₂O. The resulting mixture was then heated in a 2.5 l autoclavewhile stirring with a heat ramp of 40° C./h to 140° C. and held at thattemperature for 15 hours. The crystallized product was then suctionfiltered and repeatedly washed distilled water. The crystalline solidwas then dried at 120° C. for 16 h, thus affording 96 g of a whitecrystalline product.

Elemental analysis of the crystalline product of Example 12 affordedNa:SiO₂:Al₂O₃ molar ratios of 2.4:11.0:1.

In FIG. 12, the XRD of the crystalline product of Example 12 isdisplayed, including the 2 Theta values and respective intensities forthe individual reflections. Additional weak reflections stemming frommordenite side-product are visible in the powder-diffraction pattern.

Thus, by using sodium-water glass instead of fumed silica, thecrystallization time may be considerably reduced.

Example 13

0.474 kg of NaAlO₂ were dissolved while stirring in 15 l of H₂O. 15.27kg of sodium-water glass and 1.17 kg of zeolite Beta seeds (commerciallyobtained from Zeolyst International) suspended in 2.53 l H₂O were thenadded, thus affording an aluminosililcate gel with a molar ratio of40.28 SiO₂:1.50 Al₂O₃:14.01 Na₂O:936.6 H₂O. The resulting mixture wasthen heated in an autoclave while stirring (at about 150 rpm) with aheat ramp of 36° C./h to 140° C. and held at that temperature for 15hours. The crystallized product was then pressure filtered and washedthree times with 35 l of distilled water, respectively. The crystallinesolid was then dried at 100° C. for 2 d, thus affording 1.1 kg of awhite crystalline product.

Elemental analysis of the crystalline product of Example 13 affordedNa:SiO₂:Al₂O₃ molar ratios of 3.53:12.1:1.

In FIG. 13a , the XRD of the crystalline product of Example 13 isdisplayed, including the 2 Theta values and respective intensities forthe individual reflections. Additional weak reflections stemming frommordenite side-product are visible in the powder-diffraction pattern.

FIGS. 13b and 13c display SEM-images of the crystalline product ofExample 13.

Example 14

19.1 g of NaAlO₂ were dissolved in 706.5 ml of H₂O. 923.6 g ofsodium-water glass and 48.0 g of zeolite Beta seeds (commerciallyobtained from Zeolyst International) were then added, thus affording analuminosililcate gel with a molar ratio of 40.28 SiO₂:1.0 Al₂O₃:13.34Na₂O:734 H₂O. The resulting mixture was then heated in a 2.5 l autoclavewhile stirring with a heat ramp of 40° C./h to 120° C. and held at thattemperature for 57 hours. The crystallized product was then suctionfiltered and repeatedly washed distilled water. The crystalline solidwas then dried at 120° C. for 16 h, thus affording 85 g of a whitecrystalline product.

In FIG. 14, the XRD of the crystalline product of Example 14 displayedtogether with both the line pattern of zeolite Beta as synthesized withan organic template as the structure directing agent, and the linepattern of mordenite.

Example 15 Isomorphous Substitution with Fe

1.34 g of NaAlO₂ and 6.54 g of NaOH were dissolved in 142.23 ml of H₂O,followed by addition of 1.69 g of zeolite Beta seeds (commerciallyobtained from Zeolyst International) and 1.35 g Fe₃(NO₃)₃.9H₂O. 16.87 gof fumed silica (Aerosil® 200) was then added to the mixture in portionswhile stirring during 30 min, after which the mixture was stirred for anadditional 30 min, thus affording an aluminosililcate gel with a molarratio of 40.28 SiO₂:1.00 Al₂O₃:13.06 Na₂O:0.5 Fe:1132.32 H₂O. The gelmixture was then transferred into a Teflon®-lined autoclave andcrystallized at 140° C. for 48 h. After having let the reaction mixturecool to room temperature, it was filtered, repeatedly washed withdistilled water, and then dried at 120° C. for 16 h, thus affording acrystalline product.

Electron Probe Micro Analysis of the crystalline product of Example 15via Energy Dispersive X-Ray Spectroscopy (EDXS) afforded Na:SiO₂:Al₂O₃molar ratios of 3.3:12.0:1 and an SiO₂:Fe molar ratio of 30.7.

In FIG. 15a , the XRD of the crystalline product of Example 15 isdisplayed, including the 2 Theta values and respective intensities forthe individual reflections. Additional weak reflections stemming frommordenite side-product are visible in the powder-diffraction pattern.

FIGS. 15b and 15c display SEM-images of the crystalline product obtainedaccording to Example 15.

We claim:
 1. A zeolitic material, comprising: a BEA framework structurewhich has two peaks, each having an intensity of from 11 to 34% in the2θ range of 25.0 to 25.8° in an XRD pattern obtained with K alpha 1wavelength of Cu; wherein the intensity relates to a peak at adiffraction angle 2θ/° of 22.12 to 22.32 as 100%, the as synthesizedzeolitic material is free of an organotemplate, and is obtained by anorganotemplate-free process comprising: (1) preparing a mixturecomprising seed crystals having a BEA framework structure, at least onesource for YO₂, and optionally, at least one source of X₂O₃; and (2)crystallizing the mixture to obtain the zeolitic material, wherein Y isa tetravalent element, and X is a trivalent element, and the zeoliticmaterial optionally comprises at least one alkali metal M.
 2. Thezeolitic material according to claim 1, wherein Y is at least oneselected from the group consisting of Si, Sn, Ti, Zr, and Ge.
 3. Azeolitic material, comprising: a BEA framework structure, having anX-ray diffraction pattern comprising at least the following reflections:Diffraction angle 2θ/° Intensity (%) [Cu K(alpha 1)] [12-32][21.07-21.27] 100 [22.12-22.32] [14-34] [25.01-25.21] [12-32][26.78-26.98] [14-34] [28.39-28.59] [28-48] [29.24-29.44] [10-30][30.00-30.20] [11-31] [32.86-33.26] [13-33] [42.90-43.30]

wherein 100% relates to the intensity of the maximum peak in the X-raypowder diffraction pattern, wherein the BEA framework structurecomprises YO₂ and optionally comprises X₂O₃, wherein Y is a tetravalentelement, and X is a trivalent element, wherein the zeolitic materialoptionally comprises at least one alkali metal M, and the as synthesizedzeolitic material is free of an organotemplate.
 4. The zeolitic materialaccording to claim 3, wherein the BEA framework structure comprisesX₂O₃, and a YO₂:X₂O₃ molar ratio is from 3 to
 20. 5. The zeoliticmaterial according to claim 4, wherein a molar ratio of alkali metalM:X₂O₃ is from 1 to
 5. 6. The zeolitic material according to claim 4,wherein X is at least one selected from the group consisting of Al, B,In, and Ga.
 7. The zeolitic material according to claim 4, wherein aportion of the Y atoms and/or of the X atoms in the BEA frameworkstructure is isomorphously substituted by at least one element selectedfrom the group consisting of Cu, Co, Cr, Ni, Fe, V and Nb.
 8. Thezeolitic material according to claim 7, wherein a molar ratio of YO₂ tothe at least one element is from 20 to
 70. 9. The zeolitic materialaccording to claim 3, wherein Y is at least one selected from the groupconsisting of Si, Sn, Ti, Zr, and Ge.
 10. The zeolitic materialaccording to claim 3, comprising an alkali metal, wherein the alkalimetal is at least one of sodium and potassium.
 11. The zeolitic materialaccording to claim 10, wherein a portion of the alkali metal atoms M issubstituted by at least one cation and/or cationic element.
 12. Thezeolitic material according to claim 3, wherein the BET surface area ofthe zeolitic material determined according to DIN 66131 is from 400 to650 m²/g.
 13. The zeolitic material according to claim 3, wherein theBEA framework structure comprises zeolite Beta.
 14. A synthetic processfor the production of the zeolitic material of claim 3, comprising: (1)preparing a mixture comprising seed crystals, at least one source forYO₂; and (2) crystallizing the mixture, wherein Y is a tetravalentelement, and X is a trivalent element, wherein the zeolitic materialoptionally comprises at least one alkali metal M, wherein when the BEAframework additionally comprises X₂O₃, the mixture according to step (1)comprises at least one source for X₂O₃, and wherein the seed crystalscomprise zeolitic material having a BEA framework structure, and noorganotemplate is added to the mixture.
 15. The process according toclaim 14, wherein the at least one source for YO₂ comprises at least onesilicate.
 16. The process according to claim 15, wherein the silicate iswater glass.
 17. The process according to claim 14, wherein the preparedmixture comprises X₂O₃ and X is at least one selected from the groupconsisting of Al, B, In, and Ga.
 18. The process according to claim 17,wherein the X₂O₃ comprises an aluminate salt.
 19. The process accordingto claim 18, wherein the aluminate salt is at least one of sodiumaluminate and potassium aluminate.
 20. The process according to claim17, wherein a YO₂:X₂O₃ molar ratio is from 20/1 to 55/1.
 21. The processaccording to claim 17, wherein the mixture of (1) further comprises atleast one source of at least one element suitable for isomorphoussubstitution of a portion of at least one of the Y atoms and the X atomsin the BEA framework structure.
 22. The process according to claim 21,wherein the molar ratio of YO₂ to the at least one element suitable forisomorphous substitution of a portion of at least one of the Y atoms andthe X atoms in the BEA framework structure is from 40 to
 100. 23. Theprocess according to claim 14, wherein an amount of seed crystals in themixture is from 1 to 35 wt.-% based on 100 wt.-% of YO₂.
 24. The processaccording to claim 14, wherein the mixture of (1) further comprises asolvent.
 25. The process according to claim 24, wherein the solventcomprises water and wherein a H₂O:YO₂ molar ratio is from 7/1 to 45/1.26. The process according to claim 14, wherein the mixture furthercomprises at least one source for OH⁻.
 27. The process according toclaim 26, wherein an OH⁻:YO₂ molar ratio of the mixture according to (1)is from 0.3 to 0.7.
 28. The process according to claim 14, wherein thezeolitic material comprises at least one alkali metal M, and wherein aM:YO₂ molar ratio in the mixture (1) is from of 0.2 to
 1. 29. Theprocess according to claim 28, wherein the YO₂:X₂O₃:M molar ratios inthe mixture (1) are from (20-55):1:(11-40).
 30. The process according toclaim 14, wherein the crystallization in comprises heating of themixture.
 31. The process according to claim 30, wherein thecrystallization is conducted under solvothermal conditions.
 32. Theprocess according to claim 30, wherein the crystallization comprisesheating of the mixture for a period ranging from 10 to 16.5 h.
 33. Theprocess according to claim 14, wherein the crystallization comprisesagitating the mixture.
 34. The process according to claim 14 furthercomprising at least one of the following (3) isolating the zeoliticmaterial having a BEA framework structure, (4) washing the zeoliticmaterial having a BEA framework structure, (5) drying the zeoliticmaterial having a BEA framework structure, and (6) subjecting thezeolitic material having a BEA framework structure to an ion-exchangeprocedure, wherein the operations (3) and/or (4) and/or (5) and/or (6)can be conducted in any order.
 35. The process according to claim 34,wherein operation (6) is conducted and at least one ionic non-frameworkelement contained in the zeolitic material having a BEA framework ision-exchanged.
 36. The process according to claim 14, wherein thezeolitic material having a BEA framework structure formed compriseszeolite Beta.
 37. The process according to claim 14, wherein the seedcrystals comprise a zeolite Beta obtained from an organotemplate freemethod.
 38. The process according to claim 14, wherein the zeoliticmaterial is not subjected to calcination.